Substituted O-(aminosulfonyl)-glycolic anilides

ABSTRACT

New and valuable substituted O-(aminosulfonyl)-glycolic anilides and a process for controlling the growth of unwanted plants with these compounds.

United States Patent [191 Fisher et al.

[ 1 SUBSTITUTED O-(AMINOSULFONYL)-GLYCOLIC ANlLllDlES [75] Inventors:Adolf Fischer, Mutterstadt; Gerhard Hamprecht, Mannheim; DietrichMangold, Neckargemuend; Wolfgang Rohr, Mannheim, all of Germany [73]Assignee: Badische Anilin- & Soda-Fabrik Aktiengesellschaft,LudWigshafen/Rhine, Germany 22 Filed: Jan. 5, 1973 [21 Appl. No: 321,548

[30] Foreign Application Priority Data Jan. 13 1972 Germany 2201432 [52]US. Cl. 260/456 A, 71/103, 260/488 CD,

[ 1 Mar. 11, 1975 [51] Int. Cl C07c 143/02. C07C 143/08. (070 143/20[58] Field of Search 260/456 A [56] References Cited UNITED STATESPATENTS 3536,721 10/1970 Soong et a1. 260/456 A [57] ABSTRACT New andvaluable substituted O-[aminosulfonyllglycolic anilides and a processfor controlling the growth of unwanted plants with these compounds.

15 Claims, N0 Drawings 1 SUBSTITUTED O-(AMINOSULFONYL )-GLYCOLICANILIDES The present invention relates to new and valuable substitutedO-[aminosulfonyl]-glycolic anilides, their preparation and use asherbicides.

It is known to use chloroacetic acid-N- isopropylanilide as a herbicide.However, its biological action is only moderate.

We have now found that substituted [aminosulfonyH-glycolic anilides ofthe formula 0 2 l o OCH bit R NHS 2 2 R where R denotes hydrogen, alkyl,haloalkyl or cycloalkyl, R denotes phenyl and R denotes alkyl, alkenyl,alkynyl, cycloalkyl or benzyl, have a good herbicidal flCtlOn.

R may be, inter alia, methyl, ethyl, propyl, isopropyl, butyl, isobutyl,sec-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, 2-chloroethyl.

R" may be, inter alia, methyl, ethyl, propyl, isopropyl, n-butyl,isobutyl, sec-butyl, tert-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl,allyl, butenyl, pentenyl, hexenyl, propargyl, butynyl, pcntynyl,hexynyl, benzyl. As can be seen from the above exemplification, thepreferred alkyl, alkenyl, haloalkyl and cycloalkyl substituents arelower-alkyl, -alkenyl, -haloalkyl and cycloalkyl moieties of up to sixcarbon atoms.

The herbicidal action of the new compounds is par ticularly in evidenceon the following weeds:

xilU/R'tlll'HX mywxurnir/rzr slender lnxtail Amurmu/mv Alt/1. amaranthspecies lwnu jiilml wild oat limmm .rp/L brome species (/u-nnpmlium.i'P/L goosefoot species I)1t-I \-Ii.r glmnr'lulu orchardgrass Digimriusunguilmlix large crabgrass k'cliinmliluu t'rim-gulli harnyardgrassElem-I'm imIir-u goosegrass (in/lulu upurim' catchweed bedstraw Lumium.vpp, deadnettle species Luli'um .i'II/I. ryegrass species Mulrit-uriut-lrummnilla chamomile lmiit'ium .rpp, panicum spp,

Iua .iII/I. luegrass species .S'cluriu .vpp. foxtail species Siuupirurrcnsiti' wild mustard without causing damage to the crop plants:

. 6 Application rates are from 0.2 to kg of active ingredient perhectare; the compounds may be applied before sowing, or before or afteremergence of the plants.

The compounds of the invention may be prepared by reacting a substitutedglycolic anilide with a substituted amino sulfonyl chloride in thepresence of an acid acceptor, e.g., triethylamine and pyridine.

EXAMPLE 1 '0-[isopropylaminosulfonyl]-glycolicacid-N-butynl-yl-3-anilide At 0 to 5C and while stirring, a solution of333 parts 10 by weight of isopropylaminosulfonyl chloride in 80 parts byweight of dichloromethane was added to a solution of 35.5 parts byweight of glycolic acid-N-butynl-yl-3-ani1ide and 214 parts by weight oftriethylamine in 600 parts by weight of dichloromethane. After 2 hoursthe reaction mixture was successively washed with dilute hydrochloricacid, water, sodium bicarbonate solution, and again with water, and thendried with magnesium sulfate. The crude product, melting at 99 to 105C,was obtained from the organic phase upon concentration in vacuo. Thepure compound melting at 108 to l 10C may be obtained byrecrystallization from benzene.

The compound has the following structural formula:

CH 9 CH CH-NI-I-SO OCH -C-N a E C "I OH 3S The compounds listed belowmay be obtained analogously:

R N'HSO OCH CN R1 a p c H CH 119 to 121 CH3 CH 87 to 88 car, cH 84 to 86n--C H CH 5O iC;,H CH" I34 to I35 n-QH CH;X iC H CH3 sec-CH CH3CHgClCH-z CH3 CGHU CH1; H z s C C27 C2H5 CgHg, to 62 n-QH, C H i-C HC-ZHF, 76 to 77 nC H C2H5 secC H z s 60 cH cicH H, ita 5 H :i 1 CH,nC;,H 6] to 63 C2H5 n 1 a 1 a 1 7 :iH1 78 to 79 5 n c,H,, nC;,H iC,,H,,nC; H sec-C.,H,, nC.1H1 CH- ClCH nC;,H tl li :i -i

Glycolic acid-N-methylanilide A solution of 10.7 parts by weight ofN-methylaniline in 20 parts by weight of tetrahydrofuran has added toit, at to C and with stirring, a solution of 10.2 parts by weight ofl,3-dioxolane2,4-dione in parts by weight of tetrahydrofuran. Thereaction mixture was then stirred at room temperature until no morecarbon dioxide evolved, and subsequently concentrated to dryness invacuo. The crude product obtained melts at 48 to 50C; the analyticallypure compound is obtained by recrystallization from ether; m.p.: 50 to52C,

The following compounds were obtained analogously: glycolic glycolicglycolic glycolic glycolic glycolic glycolic glycolicacid-N-ethylanilide, m.p. 39 to 41C acid-N-n-propylanilide, m.p. 68 to69C acid-N-propargylanilide, m.p. 69 to 71Cacid-N-3-methylbutyn-l-yl-3-anilide acid-N-allylanilideacid-N-buten-l-yl-3-anilide acid-N-3-methylbuten-l-yl-3-anilideacid-N-cyclohexylanilide glycolie acid-N-cyclopentylanilide glycolicacid-N-benzylanilide.

The agents according to the invention may be used as solutions,emulsions, suspensions or dusts. The form of application dependsentirely on the purpose for which the agents are being used; in any caseit should ensure a fine distribution of the active ingredient.

For the preparation of solutions to be sprayed direct, hydrocarbonshaving boiling points higher than 150C, cg. tetrahydronaphthalene oralkylated naphthalenes, or organic liquids having boiling points higherthan 150C and having one or more than one functional group. eg. the ketogroup, the ether group, the ester group or the amide group, this groupor these groups being attached as substituent(s) to a hydrocarbon chainor being a component ofa heterocyclic ring, may be used as a sprayliquids.

Aqueous formulations may be prepared from emulsion concentrates, pastesor wettable powders by adding water. To prepare emulsions theingredients as such or dissolved in a solvent may be homogenized inwater or organic solvents by means of wetting or dispersing agents,e.g., polyethylene oxide adducts. Concentrates which are suitable fordilution with water may be prepared from active ingredient, emulsifyingor dispersing agent and possibly solvent.

Dusts may be prepared by mixing or grinding the active ingredients witha solid carrier, e.g., kieselguhr, talc, clay or fertilizers.

Granules may be prepared by applying the active ingredients to solidcarriers of various particle sizes.

Adherents, oils and other herbicidal active ingredients may also beadded.

EXAMPLE 2 In the greenhouse, loamy sandy soil was filled into pots andsown with Zea mays, Soja hispida, Gossypium hirsutum, Beta vulgaris,Ec/u'noc/tloa crus-galli, Setarl'a spp., Poa trivialzlr, Brumus tectarumand Alopecurus myosuroides. The soil prepared in this manner was thentreated with 2 kg per hectare of O-(isopropylaminosulfonytlyglycolicacid-N-butyn-l-yl-3-anilide (l) and, for comparison, with 2 kg perhectare of chloroacetic acid- N-isopropylanilide (11), each activeingredient being dispersed in 500 liters of water per hectare.

After 4 to 5 weeks it was ascertained that active ingredient I had thesame good crop plant compatibility as 11, combined with a strongerherbicidal action.

The results of this experiment are given below:

= no damage 100 complete destruction EXAMPLE 3 On an agricultural plotthe plants Zea mays, Gossypium hirsutum, Soja hispida, Beta vulgaris,Ec/tinochlua crus-galli, Digitaria sanguinalis, Panicum virgarum,Eleusine indica and Poa annua were treated at a growth height of 2 to 14cm with 2 kg per hectare ofl and 2 kg per hectare ofII, each activeingredient being emulsified in 500 liters of water per hectare.

After 3 to 4 weeks it was ascertained that active ingredient 1 had notonly better crop plant compatibility than II, but also a strongerherbicidal action.

The results of this experiment are given below: Active ingredient l 11Zea mays 0 0 GOSSyPI IHN In'rsurum 0 15 Soja lzispida 5 l5 Bela vulgarix0 l0 Ec/rinoclilua crus-galli 6(1 Digimria sanguinalis 40 Panicum\irgalmn 90 40 Eleusine indica 90 30 P00 annuu 80 l 5 no damage completedestruction The action of the following compounds corresponds to thatof] above: 0-(isopropylaminosulfonyl)-glycolic acid-N-methylanilide0-(isopropylaminosulfonyl)- glycolic acid-N-isobutylanilideO-(ethylaminosulfonyl)- glycolic acid-N-butyn-l-yl-3-anilideO-(isopropylaminosulfonyl)-glycolic acid-N-sec-butylanilide EXAMPLE 4 90parts by weight of compound 1 is mixed with 10 parts by weight ofN-methyl-u-pyrrolidone. A mixture is obtained which is suitable forapplication in the form of very fine drops.

EXAMPLE 5 taining 0.02 percent by weight of the active ingredient.

EXAMPLE 6 20 parts by weight of compound I is dissolved in a mixtureconsisting of 40 parts by weight of eyclohexanone, 30 parts by weight ofisobutanol, 20 parts by weight of the adduct of 7 moles of ethyleneoxide to 1 mole of isooctylphenol, and 10 parts by weight of the adductof 40 moles of ethylene oxide to 1 mole of castor oil. By pouring thesolution into 100,000 parts by weight of water and uniformlydistributing it therein, an aqueous dispersion is obtained containing0.02 percent by weight of the active ingredient.

EXAMPLE 7 20 parts by weight of compound I is dissolved in a mixtureconsisting of 25 parts by weight of cyclohexanol. 65 parts by weight ofa mineral oil fraction having a boiling point between 210 and 280C, and10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 moleof castor oil. By pouring the solution into [00,000 parts by weight ofwater and uniformly distributing it therein, an aqueous dispersion isobtained containing 0.02 percent by weight of the active ingredient.

EXAMPLE 8 20 parts by weight of compound I is well mixed with 3 parts byweight of the sodium salt of diisobutylnaphthalene-a-sulfonic acid, 17parts by weight of the sodium salt ofa ligninsulfonic acid obtained froma sulfite waste liquor, and 60 parts by weight of powdered silica gel,and triturated in a hammer mill. By uniformly distributing the mixturein 20,000 parts by weight of water, a spray liquid is obtainedcontaining 0.1 percent by Active ingredient Crop plants:

Suja llixpizlu Gutsylium liirsulum Braxsim napux Helium/tux UIIIIUUSAllium (e m Unwanted plants:

Ecliinoch/oa ems-gall! Digimria sanguinalis Selaria faberii Pea annuaLolium mulliflorum Eleusine indica Matricaria cliamumilla no damageweight of the active ingredient.

EXAMPLE 9 3 parts by weight of compound I is intimately mixed with )7parts by weight of particulate kaolin. A dust is obtained containing 3percent by weight of the active ingredient.

EXAMPLE 10 30 parts by weight of compound I is intimately mixed completedestruction 8 with a mixture consisting of 92 parts by weight ofpowdered silica gel and 8 parts by weight of paraffin oil which has beensprayed onto the surface of this silica gel. A formulation of the activeingredient is obtained having good adherence.

EXAMPLE l1 acid-N-butynacid-N- acid-N-butyn- VII0-(isopropylaminosulfonyl)-glycolic acid-N- ethylanilide VIII0-(ethylaminosulfonyl)-glycolic acid-N- ethylanilide After 3 weeks itwas ascertained that the active ingredients exhibited good crop plantcompatibility combined with an excellent herbicidal action.

The results are given below:

VI VII 0 5 (l (l 0 (l 0 (l (l (l (I (l (l 0 0 0 (l 0 0 0 (l (l (l 0 0 00 0 (l l) O (J (l 0 (l 0 0 0 0 0 0 0 (l 0 0 0 0 (l (J 0 (l (l l ()0 l 00l 00 l 00 l 00 l 00 I00 100 l00 I00 I00 100 EXAMPLE 12 In thegreenhouse, the plants Soja hispida, Beta vulgaris, Gossypium hirsulum,()ryza saliva, Triticum aeslivum, Zea mays, Alupm'urus myusuroides,Lalium mullrflurum, Selaria fuhcrii, lz'leusim' indicu, lichinachloacrus-galli, Clu'nopodium album and Marricariu chamomilla were treated ata growth height of 2 to 16 cm with 1 kg per hectare of each ofthefollowing active ingredients I O-(isopropylaminosulfonyl)-glycolicacid-N-butynl-yl-3-anilide UNITEDSTATES PATENT AND TRADEMARK OFFICECERTIFICATE OF CORRECTIO March 11, 1975 |NVENT0R(5) 1 Adolf Fischer, etall It is certified that error appears in the above-identified patentand that said Letters Patent are hereby corrected as shown below:

PATENT NO.

'DATED In Column 2, Line 55, under the column labeled "R delete "C 7"and substitute --C H In Column 2, Line 56, under the column labeled "Rdelete "1-" In Column 3, Line 6, under the column labeled "R delete "i-"In Column 3, Line 7, under the column labeled "R delete "iC H andsubstitute --i-C H Signed and Sealed thts Seventh Day Of September 1976[SEAL] v A nest:

RUTH C. MASON Arresting Officer C. MARSHALL DANN ('vmmissl'nneruj'larenrs and Trademarks

1. A SUBSTITUTED 0-(AMINOSULFONYL)-GLYCOLIC ANILIDE OF THE FORMULA
 1. Asubstituted 0-(aminosulfonyl)-glycolic anilide of the formula 2.0-(aminosulfonyl)-glycolic acid-N-butyn-1-yl-3-anilide. 3.0-(methylaminosulfonyl)-glycolic acid-N-butyn-1-yl-3-anilide. 4.0-(ethylaminosulfonyl)-glycolic acid-N-butyn-1-yl-3-anilide. 5.0-(propylaminosulfonyl)-glycolic acid-N-butyn-1-yl-3-anilide. 6.0-(isopropylaminosulfonyl)-glycolic acid-N-butyn-1-yl-3-anilide. 7.0-(n-butylaminosulfonyl)-glycolic acid-N-butyn-1-yl-3-anilide. 8.0-(sec-butylaminosulfonyl)-glycolic acid-N-butyn-1-yl-3-anilide. 9.0-(2-chloroethylaminosulfonyl)-glycolic acid-N-butyn-1-yl-3-anilide. 10.0-(cyclohexylaminosulfonyl)-glycolic acid-N-butyn-1-yl-3-anilide. 11.0-(aminosulfonyl)-glycolic acid-N-propargylanilide. 12.0-(methylaminosulfonyl)-glycolic acid-N-propargylanilide. 13.0-(ethylaminosulfonyl)-glycolic acid-N-propargylanilide. 14.0-(propylaminosulfonyl)-glycolic acid-N-propargylanilide.